Sulfuric acid catalysis and methods of use for isomerization of hydrocarbons

ABSTRACT

Compositions containing sulfuric acid and one or more of certain chalcogen-containing compounds in which the chalcogen compound/H 2  SO 4  molar ratio is below 2 contain the mono-adduct of sulfuric acid which is catalytically active for promoting organic chemical reactions. Suitable chalcogen-containing compounds have the empirical formula ##STR1## wherein X is a chalcogen, each of R 1  and R 2  is independently selected from hydrogen, NR 3  R 4 , and NR 5 , at least one of R 1  and R 2  is other than hydrogen, each of R 3  and R 4  is hydrogen or a monovalent organic radical, and R 5  is a divalent organic radical. Such compositions are useful for catalyzing organic reactions such as oxidation, oxidative addition, reduction, reductive addition, esterification, transesterification, hydrogenation, isomerication (including racemization of optical isomers), alkylation, polymerization, demetallization of organometallics, nitration, Friedel-Crafts reactions, and hydrolysis. Novel catalysts are disclosed which involve combinations of the chalcogen compound-sulfuric compositions with one or more transition metal halides and/or with one or more surfactants. The surfactant-containing compositions are particularly useful for the treatment of materials containing lipophilic substances. Novel compositions containing a chalcogen compound-sulfuric acid component and one or more organic reactants are also disclosed.

RELATED APPLICATIONS

This application is a division of 06/771,259 filed Aug. 30, 1985 nowU.S. Pat. No. 4,722,986 which is a continuation-in-part of Ser. No.679,235, filed Dec. 7, 1984; now U.S. Pat. No. 4,589,925 Ser. No.675,774, filed Nov. 28, 1984 now U.S. Pat. No. 4,673,522; Ser. No.673,358, filed Nov. 20, 1984, now U.S. Pat. No. 4,664,717; Ser. No.673,508, filed Nov. 20, 1984, now U.S. Pat. No. 4,944,787; and Ser. No.453,496, filed Dec. 27, 1982, the last of which was a continuation inpart of Ser. No. 442,296, filed Nov. 17, 1982, now abandoned; Ser. No.444,667, filed Nov. 26, 1982, now abandoned; Ser. No. 331,001, filedDec. 15, 1981, now U.S. Pat. No. 4,402,852; Ser. No. 330,904, filed Dec.15, 1981, now U.S. Pat. No. 4,404,116; Ser. No. 318,629, filed Nov. 5,1981, now U.S. Pat. No. 4,445,925; Ser. No. 318,368, filed Nov. 5, 1981,now U.S. Pat. No. 4,447,253; and Ser. No. 318,343, filed Nov. 5, 1981,now U.S. Pat. No. 4,397,675.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of acid-catalyzed organic reactionsand particularly to methods of conducting acid-catalyzed reactions oforganic compounds which reactions are promoted by strong acids. Theinvention also relates to novel acidic compositions useful in suchreactions.

2. Description of the Art

The ability of sulfuric acid to catalyze a variety of organic reactionsis well known. It is also known that urea (a chalcogen compound usefulin this invention) and sulfuric acid will combine to form adductsincluding the monourea-sulfuric acid adduct and the diurea-sulfuric acidadduct. For instance, D. F. du Toit, Verslag Akad. Wetenschappen, 22,573-4 (abstracted in Chemical Abstracts, 8, 2346, 1914) disclosed thaturea forms certain compounds with oxalic, acetic hydrochloric, nitricand sulfuric acids. L. H. Dalman, "Ternary Systems of Urea and Acid. I.Urea, Nitric Acid and Water. II. Urea, Sulfuric Acid and Water. III.Urea, Oxalic Acid and Water"; JACS, 56, 549-53 (1934), disclosed thephase relationships between the solid phase and saturated solutionscontaining urea and sulfuric acid at 10° C. and 25° C. The SulfurInstitute, Sulfur Institute Bulletin No. 10 (1964), "Adding PlantNutrient Sulfur to Fertilizer", disclosed that urea reacts with sulfuricacid to form two complexes of "urea sulfate" which are usefulfertilizers. Methods of manufacturing certain combinations of urea andsulfuric acid are disclosed by Verdegaal et al. in U.S. Pat. No.4,310,343 and by Jones in U.S. Pat. No. 4,116,664.

A wide variety of organic conversions are catalyzed by theproton-donating ability of strong acids. Such reactions have beenextensively investigated and have been widely discussed in theliterature. For instance, the Kirk-Othmer Encyclopedia of ChemicalTechnology, Third Edition, John Wiley and Sons, New York, 1980,discusses a variety of organic reactions that are catalyzed by strongacids including mineral acids, transition metal halides such asFriedel-Crafts catalysts, conjugate Friedel-Crafts catalysts, andothers. Kirk-Othmer defines acid-catalyzed reactions as those in which aproton is transferred from the catalyst to the reactant which is therebyconverted to an unstable state which immediately leads to the reactionunder consideration. (Volume 5, page 33). While the proton donationmechanism of acid-catalyzed reactions referred to in Kirk-Othmer may ormay not account for the reactions that take place in all acid-catalyzedreactions, it is known that strong acids promote numerous reactionsincluding oxidative addition, reductive addition, esterification,transesterification, hydrogenation, isomerization (includingracemization of optical isomers), hydrolysis and alcoholisis,alkylation, olefin polymerization, Friedel-Crafts reactions,demetalization of organics, and nitration reactions, among others.Strong acids known to be capable of promoting such acid-catalyzedorganic reactions include sulfuric acid, nitric acid, hydrochloric acid,transition metal halides including the so-called Friedel-Craftscatalysts, for example, the halides of aluminum, gallium, boron,titanium, vanadium, tin and others, and conjugate Friedel-Craftscatalysts also known as Bronsted-Lewis superacid mixtures (Kirk-Othmer,V. 11, 295) such as mineral acid adducts of transition metal halides.

All of the known strong acid catalysts, and the methods involving theiruse for the promotion of acid-catalyzed organic reactions, suffer fromone or more disadvantages. For instance, the strong mineral acidspromote side reactions which form undesired by-products, destroy theorganic feed material or product, and/or consume or deactivate thecatalyst. Sulfuric acid is a strong sulfating, sulfonating, oxidizing,and dehydrating agent, and by virtue of those activities, it is consumedin most organic reactions by side reactions involving these mechanisms.Furthermore, the sulfonating and oxidizing activities of sulfuric acidresult in the sulfonation and oxidation of organic feedstocks and/orproducts. Similar deficiencies exist with the other strong mineral acidssuch as hydrochloric and nitric acids. Hydrochloric acid chlorinates thereactants and thereby consumes the feed to produce unwanted chlorinatedby-products. Nitric acid oxidizes and/or nitrates organic compounds.Hydrofluoric acid fluorinates organic reactants and products. Thetransition metal halides, including the Friedel-Crafts catalysts, aredifficult to handle in that they must be isolated from water andreducing agents. Such catalysts also halogenate organic feedstocks andproducts.

Accordingly, a need exists for improved methods of conductingacid-catalyzed organic reactions and for improved acid catalysts for usein such reactions which will promote the desired acid-catalyzed organicreaction yet reduce or eliminate the side reactions normally associatedwith acid-catalyzed organic reactions.

It is therefore a principal object of this invention to provide novelmethods for the acid-catalyzed conversion of organic compounds.

Another object is the provision of novel methods for conductingacid-catalyzed reactions of organic compounds in the presence ofcompositions which comprise sulfuric acid.

Another object of this invention is the provision of novel acidcatalysts comprising sulfuric acid which are effective for conductingacid-catalyzed.organic reactions.

Another object of this invention is the provision of novel compositionswhich are useful for conducting acid-catalyzed organic reactions.

Another object of this invention is the provision of novel catalystscomprising sulfuric acid which have improved activity in the presence oflipophilic materials.

Yet another objective of this invention is the provision of novelmethods for catalyzing organic reactions with sulfuric acid.

Another object is the provision of novel methods for the oxidativeaddition of organic compounds.

Yet another object is the provision of novel methods for reductiveaddition of organic compounds.

Another object is the provision of novel sulfuric acid-containingcompositions useful for conducting organic reactions.

Another object is the provision of novel methods for the esterificationand transesterification of organic compounds.

Yet another object of this invention is the provision of novel methodsfor hydrogenating organic compounds containing olefinic unsaturation.

Another object is the provision of novel methods for isomerizing organiccompounds.

Yet another object is the provision of novel methods for the hydrolysis,alcoholisis, thiolosis, and amination of organic compounds.

Another object is the provision of novel methods for the alkylation oforganic compounds.

Yet another object is the provision of novel methods for polymerizingolefinic compounds.

Yet another object is the provision of novel conjugate Friedel-Craftscatalysts.

Another object is the provision of novel Friedel-Crafts catalyzedorganic reactions.

Yet another object of this invention is the provision of novel methodsfor demetalizing organic compounds.

Another object is the provision of novel methods for nitrating organiccompounds.

Other objects, aspects and advantages of this invention will be apparentto one skilled in the art in view of the following disclosure and theappended claims.

SUMMARY OF THE INVENTION

Briefly, the invention provides novel (1) surfactant-containing catalystcompositions suitable for promoting acid-catalyzed organic reactions,(2) conjugate Friedel-Crafts acid catalysts suitable for promotingacid-catalyzed organic reactions, (3) reactant-containing compositionscontaining a chalcogen-containing compound, sulfuric acid, and one ormore reactants useful for conducting organic reactions, and (4) methodsof conducting acid-catalyzed organic reactions.

It has been discovered that compositions which contain one or more ofcertain chalcogen-containing compounds and sulfuric acid and in whichthe molar ratio of chalcogen compound to sulfuric acid is less than 2are highly useful as catalysts, particularly for organic reactions.Within this range of molar ratios, at least a portion of the sulfuricacid will be in the form of the mono adduct of sulfuric acid, whichadduct is the active acid catalyst useful herein. The usefulchalcogen-containing compounds have the empirical formula ##STR2##wherein X is a chalcogen, each of R₁ and R₂ is hydrogen, NR₃ R₄ or NR₅,at least one of R₁ and R₂ being other than hydrogen, each of R₃ and R₄is hydrogen or a monovalent organic radical, and R₅ is a divalentorganic radical.

Among the novel catalysts of the present invention are compositionscontaining the chalcogen compound-sulfuric acid component in combinationwith a surfactant and/or solvent. Such catalysts are especially usefulfor promoting chemical reactions involving relatively lipophilic organicmaterials, since surfactants and/or solvents accentuate the activity ofthe chalcogen compound-acid component toward such materials.

Also provided in the invention are conjugate Friedel-Crafts catalystscontaining combinations of the chalcogen compound-sulfuric acidcomponent described above, with or without surfactant, and one or moretransition metal halides.

Novel reactant-containing compositions are also provided containing thedescribed chalcogen compound-sulfuric acid component, with or without asurfactant, and one or more reactants which are useful in conductingorganic reactions.

The novel methods of this invention involve acid-catalyzed reactions ofone or more organic compounds in the presence of the describedcatalysts. The solvent and/or surfactant-containing catalysts areparticularly useful for many acid-catalyzed organic reactions,particularly those in which the more lipophilic, i.e., hydrophobicmaterials are present. It has been found that surfactants and solventsaccentuate the activity of the chalcogen-acid component toward morelipophilic substrates. Similarly, the novel conjugate acid catalysts canbe employed in the novel methods of this invention.

In particular, the novel methods of this invention involve theconversion of organic materials, at least in part, by the acid-catalyticactivity of sulfuric acid. Thus, they include all acid-catalyzed organicreactions that are catalyzed by sulfuric acid, such as

(a) oxidation of one or more organic compounds in the presence of anoxidant;

(b) reduction of one or more organic compounds by reaction with areducing agent such as hydrogen;

(c) hydrolysis of one or more organic compounds by reaction with waterand/or one or more alcohols and/or thiols;

(d) oxidative addition of one or more organic compounds by reaction withan oxidant; .

(e) reductive addition of organic compounds by reaction with a reducingagent;

(f) esterification of amides, nitriles, carboxylic acids, acyl halides,thiocarboxylic acids, and/or carboxylic acid anhydrides by reaction withalcohols and/or thiols;

(g) hydrogenation of organic compounds containing carbon-to-carbonunsaturation by reaction with hydrogen;

(h) alkylation of organic compounds by reaction with an organicalkylating agent having at least one carbon-to-carbon olefinic bond;

(i) polymerization of organic compounds containing olefinic unsaturationin the presence of an oxidant;

(j) Friedel-Crafts reactions of organic compounds with hydrocarbylhalides;

(k) isomerization of hydrocarbons having four to about twenty carbonatoms per molecule;

(l) demetalization or organo-metal compounds by reaction with waterand/or alcohols; and

(m) nitration of organic compounds by reaction with a nitrating agentsuch as nitric oxide.

The methods and compositions of this invention eliminate most, if notall, of the deficiencies associated with the acid-catalyzed conversionof organic compounds in the presence of sulfuric acid. The chalcogencompound-sulfuric acid components minimize or completely eliminate theundesirable oxidizing, dehydrating and sulfonating activity of sulfuricacid yet retain the acid's strong proton donating ability. Thus, thesulfuric acid contained in the chalcogen compound-acid component is notdestroyed during acid-catalyzed organic reactions due to sulfonation,oxidation or other reactions associated with sulfuric acid. At the sametime, organic feed materials are not destroyed or converted toundesirable by-products by the side reactions usually associated withsulfuric acid. All of these benefits exist with all forms of chalcogencompound-sulfuric acid components employed in the methods of thisinvention, including the novel surfactant-containing catalysts and thenovel conjugate transition metal halide catalysts. Moreover, the solventand surfactant-containing catalysts exhibit improved catalytic activityfor the conversion of organic compounds in accordance with the methodsof this invention, particularly for the conversion of more lipophiliccompounds and of organic materials which contain lipophilic matter, suchas fats, waxes, and higher molecular weight organic substances.

Without intending to be constrained to any particular theory, it ispresently believed that adducting sulfuric acid with compounds, such asthe described chalcogen compounds, capable of donating electrons to thesulfuric acid modifies the lability of the acid hydrogens in a mannerwhich inhibits the acid's propensity for undesired side reactions.Stronger electron donors are believed to inhibit acid hydrogen liabilityto a greater extent as does the addition of two, rather than one,chalcogen molecules to each acid molecule. For instance, the monoureaadduct of sulfuric acid is a selective, active acid catalyst while thediurea adduct is essentially inactive as an acid catalyst.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides novel (1) surfactant-containing chalcogencompound-sulfuric acid combinations which are effective acid catalystsfor promoting organic conversions, (2) conjugate Friedel-Craftscatalysts which comprise combinations of transition metal halides andthe described chalcogen compound-acid components, (3) compositionscontaining the described novel catalysts of this invention, with orwithout surfactant, and one or more reactants, which reactants areuseful in conducting organic reactions, and (4) methods of conductingacid-catalyzed organic reactions, particularly organic reactions knownto be catalyzed by sulfuric acid.

The chalcogen compound-sulfuric acid components useful in the methods ofthis invention contain a combination of sulfuric acid and one or more ofcertain chalcogen compounds in which the molar ratio of the chalcogencompound to sulfuric acid is below 2. Within this range of molar ratios,at least a portion of the sulfuric acid is present as the mono-adduct ofsulfuric acid. In one embodiment, the chalcogen compound-acid componentmay optionally contain a surfactant, solvent or other components.Surfactants and solvents increase the activity of the acid componenttoward organic materials, particularly toward organic materials thatcontain lipophilic constituents such as fats, oils, waxes and the like.The chalcogen compound-sulfuric acid component, with or withoutsurfactant, may also be combined with one or more organic or inorganicreactants which participate in the desired organic reaction to form acomposition useful in conducting the desired organic reaction. Inanother embodiment, the chalcogen-acid component, with or withoutsurfactants, can be combined with a conventional transition metal halidecatalyst to form a conjugate Friedel-Crafts catalyst useful in thesemethods.

The methods of this invention involve the acid-catalyzed conversion oforganic compounds. In particular, these methods can be employed for theacid-catalyzed conversion of any organic material that can be convertedby sulfuric acid catalysis, and usually without the occurrence ofundesirable side reactions normally associated with sulfuric acid.Illustrative of suitable acid-catalyzed reactions are oxidation,particularly oxidative addition; esterfication; transesterification;hydrogenation, isomerization, including racemization of optical isomers;hydrolysis and alcoholisis by reaction with water, alcohols, or thiols;alkylation; olefin polymerization; Friedel-Crafts reactions;demetalization; and nitration. In accordance with these methods, theorganic reactant (or reactants) is contacted with the chalcogencompound-sulfuric acid component in the form of a solution in water orother solvents, or as a molten mixture of chalcogen compound andsulfuric acid.

The chalcogen compound-sulfuric acid components are reaction products ofsulfuric acid and one or more of certain chalcogen-containing compoundsin which the molar ratio of chalcogen compound to sulfuric acid is below2. In such components, at least a portion of the sulfuric acid ispresent as the mono-adduct of sulfuric acid and the chalcogen compound.These components may be employed in the methods disclosed herein, asmelts, as solutions of such mixtures in water or other solvents, or assolids in which the chalcogen compound-sulfuric acid component isimpregnated or exchanged into a solid support such as carbon, refractoryoxides such as silica, alumina, and the like, acid or basic ion exchangeresins or zeolites such as the natural and synthetic aluminosilicates,and combinations of such supports. The catalysts may also containoptional components such as surfactants and transition metal halides.Other components that do not substantially negate the proton-donatingactivity of the monoadduct of sulfuric acid may also be present.

The useful chalcogen-containing compounds have the empirical formula##STR3## wherein X is a chalcogen, R₁ and R₂ are independently chosenfrom hydrogen, NR₃ R₄ or NR₅, with at least one of R₁ and R₂ being otherthan hydrogen, R₃ and R₄ are independently chosen from hydrogen or amonovalent organic radical, and R₅ is a divalent organic radical. One ofthe monovalent radicals R₃ and R₄ can be hydrogen, and either or both ofR₃ and R₄ can be any organic radical including alkyl, aryl, alkenyl,alkenylaryl, aralkyl, aralkenyl, cycloakyl, cycloalkenyl, or alkynyl,which can be unsubstituted or substituted with pendant functional groupssuch as hydroxyl, carboxyl, oxide, thio, thiol, or others, and they cancontain acyclic or cyclic heteroatoms such as oxygen, sulfur, nitrogen,or others. R₅ can be any divalent organic radical such as alkdyl, ardyl,alkenydyl, alkyndyl, aralkdyl, aralkendyl, which may contain pendantatoms or substituents and/or acyclic or cyclic heteroatoms as describedfor R₃ and R₄. Preferably, both R₁ and R₂ are other than hydrogen, bothR.sub. 3 and R₄ are selected from hydrogen or hydrocarbyl radicalswhich, in combination, contain about 10 carbon atoms or less, and X ispreferably oxygen or sulfur, most preferably oxygen. Such substituentsare presently preferred due to their relatively higher chemicalstability. Particularly preferred chalcogen-containing compounds areurea, thiourea, formamide, and combinations of these.

The chalcogens are elements of Periodic Group VI-B and include oxygen,sulfur, selenium, tellurium, and polonium. Oxygen and sulfur arepresently preferred due to low cost, availability, low toxicity andchemical activity, and oxygen is the most preferred.

The chalcogen compound-sulfuric acid components may contain unreacted(free) sulfuric acid or the di-adduct of sulfuric acid. Useful andpreferred proportions of chalcogen compound, sulfuric acid, and of themono- and di-adducts of sulfuric acid, relative to each other, can beconveniently expressed in terms of the chalcogen compound/sulfuric acidmolar ratio. This ratio will be below 2, usually within the range ofabout 1/4 to about 7/4, preferably about 1/2 to about 3/2, and mostpreferably between about 1/1 and about 3/2. Molar ratios within therange of about 1/4 to about 7/4 define compositions in which at least 25percent of the sulfuric acid is present as the mono-adduct of sulfuricacid. Molar ratios within the range of 1/2 to about 3/2 definecompositions in which at least 50 percent of the sulfuric acid ispresent as the mono-adduct. The most preferred molar ratio range ofabout 1/1 to about 3/2 defines compositions which contain essentially nouncomplexed sulfuric acid and in which at least 50 percent of thesulfuric acid is present as the mono-adduct of sulfuric acid. The mostpreferred combinations have chalcogen compound/sulfuric acid molarratios of about 1/1. In such compositions essentially all of thesulfuric acid is present as the mono-adduct of sulfuric acid, and suchcompositions are essentially free of uncomplexed sulfuric acid.Substantial amounts of uncomplexed sulfuric acid, i.e., sulfuric acidthat is not complexed with a chalcogen compound as either the mono-ordi-adduct, are less preferred since sulfuric acid, when present insubstantial amounts, may promote side reactions such as oxidation,sulfonation, dehydration and/or other reactions. While the di-adduct isgenerally not detrimental to the performance of the mono-adductcomponents as acid catalysts for organic reactions, it has little or noproton-donating ability and thus little or no activity as a catalyst foracid-catalyzed organic reactions.

Useful solutions contain a catalytically active amount of themono-adduct of sulfuric acid in a suitable solvent. Very low mono-adductconcentrations, e.g., on the order of about 0.5 weight percent of thesolution (or melt), are sufficient to promote a variety ofacid-catalyzed organic reactions. However, higher concentrations of themono-adduct are generally preferred. Thus, the solutions will usuallycontain at least 0.5, generally at least about 1, preferably at leastabout 5, and most preferably at least about 10 weight percent chalcogencompound and sulfuric acid based on the combined weight of those twocomponents. Higher concentrations of chalcogen compound and sulfuricacid provide increased catalytic activity. For instance, solutionscontaining at least 50 percent, and even 85 weight percent or more ofthe combination of chalcogen compound and sulfuric acid, in combination,will usually constitute 0.5 to about 90, normally about 1 to about 90,and preferably about 5 to about 90 weight percent of the solution.

Any solvent suitable for dissolving the chalcogen compound-sulfuric acidcomponent under the reaction conditions can be employed. Suitablesolvents include polar solvents such as water, dimethylsulfoxide (DMSO),halogenated hydrocarbons such as trichloromethane, oxygenatedhydrocarbons such as methylethylketone and tetrahydrofuran, and thelike. The solvent is preferably not reactive with the chalcogencompound-sulfuric acid component, the organic feed, intermediates orproducts, or other components employed in the acid-catalyzed organicreactions unless, or course, the organic feed is also employed as thesolvent for the urea-sulfuric acid component.

When water is employed as the only solvent, or as a component of thesolvent, I have observed that, at relatively high water concentrations,water begins to displace the chalcogen compound as an adduct on thesulfuric acid thereby, in a manner of speaking, releasing free sulfuricacid into the system. This process is reversible; i.e., as water isremoved from the system the chalcogen compound-sulfuric acid adductreforms. For these reasons, the presently preferred compositions andcatalyst systems have H₂ O/(chalcogen compound +H₂ SO₄) molar ratios ofabout 5 or less, most preferably about 2.5 or less.

Melts of the chalcogen compound-sulfuric acid component-containingcompositions that have melting points above ambient temperature, e.g.,about 70° F., can also be employed to catalyze the acid-catalyzedorganic reactions. The active components useful in this embodiment aresolids at ambient temperature and are converted to melts by heating themto elevated reaction temperatures. Within this embodiment, the meltswill usually contain at least about 50, and preferably at least about 80weight percent of the chalcogen compound-sulfuric acid component basedon the combined weight of chalcogen compound and sulfuric acid. Themelts will usually contain at least about 20, generally at least about50, preferably at least about 80, weight percent of the preferredmono-adduct of sulfuric acid.

The compositions employed in the methods of this invention may alsocontain one or more surfactants which are preferably, although notnecessarily, chemically stable for a significant period of time in thepresence of the acid adduct component and in the presence of othercomponents employed in the methods of this invention. Surfactantsincrease the activity of the acid adduct toward essentially allnon-polar organic compounds including lipophilic organic materials suchas waxes, proteins, ligands, fats, alkanes, high molecular weight acids,alcohols, and the like. For instance, surfactants enhance the activityof the liquid acid adduct compositions toward cellulosic material suchas growing or harvested vegetation which is coated with or whichcontains a significant amount of waxy cuticle. Thus, surfactants enhancethe acid-catalyzed hydrolysis of lipid-containing cellulosic materialsand increase the herbicidal activity of the urea-sulfuric acid componenttoward growing vegetation as discussed hereinafter and in my copendingapplication Ser. No. 444,667 referred to above and incorporated hereinby reference in its entirety. The herbicidal activity of the describedchalcogen compound-sulfuric acid components is apparently due, at leastin part, to their ability to catalyze the chemical conversion ofcellulose and/or other organic compounds in plant matter. As describedherein, these chalcogen compound-sulfuric acid components are capable ofcatalyzing reactions involving organic compounds other than plantmatter, as well.

The selected surfactant is preferably sufficiently chemically stable inthe liquid or solid compositions, or in the melts formed from the solidcompositions, to assure that the surfactant retains sufficient wettingability toward the organic material to be converted, for a period oftime required to manufacture, store, transport and employ the chalcogencompound-sulfuric acid component. The stability of any surfactant can bereadily determined by adding an amount of the surfactant to thechalcogen compound-sulfuric acid composition in which it is to beemployed and monitoring the combination by conventional nuclear magneticresonance (NMR) analytical techniques. NMR can be used to monitor thefrequency and magnitude of spectral peaks characteristic of a selectednucleus, e.g., a hydrogen nucleus in the surfactant. Persistent spectralpeak magnitude and frequency over a period of 5 to 6 hours indicatestability. Diminished peak magnitude, or a shift in peak frequencyassociated with the selected nucleus, indicates instability, i.e., thatthe arrangement of functional groups in the surfactant molecule has beenmodified.

Illustrative of classes of stable surfactants are nonionics such as thealkylphenol polyethylene oxides, anionics such as the long chain alkylsulfates, and cationics such as 1-hydroxyethyl-2-heptadecenylgloxalidin. Of these, the polyethylene oxide nonionic surfactants areparticularly preferred. Illustrative of preferred specific surfactantsis the nonionic surfactant marketed by Thompson-Hayward, Inc., under thetrademark T-MULZ 891.

The surfactant concentration is preferably sufficient to increase thewetting ability of the chalcogen compound-acid component for the organicmaterial to be converted. Even very minor surfactant concentrationsincrease the wetting ability of the acid-adduct component to someextent. Surfactant concentration will usually be at least about 0.05,generally at least about 0.1, and preferably at least about 0.2 weightpercent of the solution as it is employed in the methods of thisinvention. Surfactant concentrations of about 0.2 to about 1 weightpercent are adequate in most applications.

The chalcogen compound-sulfuric acid component can be combined withtransition metal halides to form the conjugate acid of the acid adductwith the transition metal halide. Such conjugate acids of transitionmetal halides, such as Friedel-Crafts catalysts and the transition metalhalides employed in the so-called Zeigler catalysts, are discussed inthe Kirk-Othmer publication referred to above and in U.S. Pat. Nos.4,078,832, 3,987,123, 4,086,062 and 4,008,360, all of which areincorporated herein by reference in their entireties. For instance, atpage 856 of Volume 12, Kirk-Othmer describes the complex of hydrochloricacid with aluminum trichloride. The transition metal halide component ofthe conjugate acid Friedel-Crafts catalysts of this invention cancomprise halides of any transition metal, particularly the halides ofaluminum, vanadium, boron, titanium, tin, gallium, and combinationsthereof. The halide component can be selected from chloride, bromide,fluoride and iodide, although the iodides are less active for thepromotion of acid-catalyzed organic reactions and, accordingly, are lesspreferred. The conjugate Friedel-Crafts catalysts of this invention cancomprise equi-molar amounts of the mono-adduct of sulfuric acid plus thetransition metal halide, or they can comprise an excess of either one ofthese two components. It is presently preferred, however, that theconjugate acid contain about 0.1 to about 2 moles of transition metalhalide for each mole of the mono-chalcogen compound-sulfuric acidadduct.

The useful chalcogen compound-sulfuric acid components can be producedby the reaction of the chalcogen compound with sulfuric acid by themethods described in my copending application Ser. No. 318,629 filedNovember 5, 1981, now U.S. Pat. No. 4,445,925, the disclosure of whichis incorporated herein by reference in its entirety. That patentdescribes, in part, the manufacture of urea-sulfuric acid componentswhich are free of decomposition products of urea, sulfuric acid, and themono- or diurea sulfuric acid adduct, and are particularly preferred forproducting the chalcogen compound-sulfuric and components of thisinvention. As described in U.S. Pat. No. 4,445,925, the reaction of ureaand sulfuric acid is extremely exothermic and, if not adequatelycontrolled, can result in the decomposition of reactants or products andthe formation of decomposition products such as sulfamic acid, ammoniumsulfamate, ammonium sulfate, and other materials. Reactions of sulfuricacid with other chalcogen compounds useful in this invention are alsoexothermic, and similar precautions should be observed, particularly inthe manufacture of more concentrated solutions and melts. The formationof such decomposition products, and the presence of such decompositionproducts in the compositions and methods of this invention, isunpreferred for several reasons. Such decomposition products mayinterfere with the acid-catalyzed conversion of organic compounds, ormay result in impurities in the finished product. Decomposition alsoresults in the loss of active sulfuric acid which must be available tocombine with the useful chalcogen compounds to produce the activemono-adduct of sulfuric acid.

Solid chalcogen compound-sulfuric acid components useful in producingthe melts and solutions of this invention can be obtained bycrystallization from their respective aqueous solutions, as describedfor urea-sulfuric acid components in my copending application Ser. No.444,667, "Methods for Controlling Vegetation," filed Nov. 26, 1982 andmy copending application Ser. No. 673,508 filed Nov. 20, 1984 for"Thermally Stable Urea-Sulfuric Acid Compositions and Methods ofManufacture," the disclosures of which are corporated herein byreference in their entireties. The surfactant, when present, will eithercrystallize (as described in Ser. No. 444,667) at approximately the sametemperature as the chalcogen compound-sulfuric acid component or will beentrained with the crystallized sulfuric acid adduct. In thealternative, the surfactant can be added, when desired, to the dry ordamp, crystallized chalcogen compound-sulfuric acid component by anysuitable mixing technique.

As described in my copending application Ser. No. 444,667, theurea-sulfuric acid aqueous solution there referred to as 18-0-0-17.has acrystallization temperature of 50° F. Designations such as 18-0-0-17 areconventionally used in the agricultural industry to define the weightpercentages of nitrogen, phosphorus, potassium and a fourth component,in this case sulfur, contained in a composition. Thus 18-0-0-17 contains18 weight percent nitrogen as urea, 0 percent phosphorus, 0 percentpotassium, and 17 weight percent sulfur. The 18-0-0-17 solution has aurea/sulfuric acid molar ratio of about 1.2 and contains about 90 weightpercent of a combination of urea and sulfuric acid. Urea and sulfuricacid, in combination, constitute 80 weight percent of the aqueoussolution designated as 10-0-0-19 in copending application Ser. No.444,667, which composition has a urea/sulfuric acid molar ratio of about0.6 and which crystallizes at about 42° F. The aqueous solutiondesignated as 9-0-0-25 comprises approximately 96 weight percent of acombination of urea and sulfuric acid, has a urea/sulfuric acid molarratio of about 0.4, and crystallizes at 14° F. The indicatedcrystallization temperatures of the three urea-sulfuric acid aqueoussolutions referred to immediately above, and the crystallizationtemperatures for other formulations of urea and sulfuric acid useful inthe composition and methods of this invention, are illustrated, in part,by the isotherms in the ternary phase diagram for urea, sulfuric acidand water in the drawing accompanying copending application Serial No.444,667. The crystallization temperatures for other urea-sulfuric acidcombinations and for combinations of sulfuric acid and other chalcogencompounds useful in the compositions and methods of this invention canbe determined from that drawing or by cooling the selected solutionuntil crystallization occurs. The crystallized material can be separatedfrom the supernatant aqueous phase by any suitable solid-liquidseparation technique such as filteration, centrifugation, decanting, andthe like, and the recovered damp solid can be dried by evaporation ifdesired.

Since lower crystallization temperatures are required to separate thedesired chalcogen compound-sulfuric acid component from the more dilutesolutions, it is preferable to begin with more concentrated solutionshaving higher crystallization points such as the 18-0-0-17 urea-sulfuricacid compositions which contains only about 10 percent water. Moreconcentrated solutions, and those having higher crystallizationtemperatures, e.g., 77° F., are even more preferred since less coolingis required to obtain a similar quantity of the chalcogencompound-sulfuric acid component.

Substantially anhydrous solid compositions can be obtained by washingthe dried, crystallized chalcogen compound-sulfuric acid component witha strongly hydrophillic solvent such as absolute ethanol or acetone. Tento 100 weight parts solvent per weight part solute are usually adequatefor this purpose. The procedures for making substantially anhydrousurea-sulfuric acid components which contain about one weight percentwater or less and are more thermally stable than more hydrouscompositions are discussed in my copending application Ser. No. 673,508referred to above. Such procedures can be employed to make otherthermally stable, anhydrous chalcogen compound-sulfuric acid componentsuseful herein.

The anhydrous mono-adduct-containing components are stable at ambientconditions and have negligible vapor pressure up to their decompositiontemperatures of up to 300° F. However, they decompose explosively atmuch lower temperatures in the presence of water. For instance, thehydrous urea-sulfuric acid compositions decompose at 176° F.

The most preferred solid urea composition consisting of the 1/1urea/sulfuric acid molar adduct has a melting point of about 100° F.,and the melting point of the urea-sulfuric acid component increases asthe urea/acid ratio deviates from 1:1 in either direction in a mannerparalleling the isotherms illustrated in the drawing of Ser. No.444,667.

Liquid chalcogen compound-sulfuric acid compositions employed in themethods of this invention can be produced by any method capable ofproducing a solution of the desired composition. Thus, the surfactantand/or other components, when used, can be added to the concentratedchalcogen compound-sulfuric acid solution during or immediately afterits manufacture by the process described in my copending applicationSer. No. 318,624, referred to above, or such components can be added tothe chalcogen compound-sulfuric acid. solution prior to its use tocatalyze organic reactions in accordance with the methods of thisinvention. Alternatively, the optional components, when employed, can bemixed with the selected solvent before or concurrently with the solid orconcentrated chalcogen compound-sulfuric acid component. Of course,dissolution of the solid chalcogen compound-sulfuric acid compositionsdescribed above that contain the desired optional components in theselected solvent will also result in the formation of the active liquidcompositions of this invention. The melts employed in severalembodiments of this invention can be produced simply by melting theselected solid composition, either prior to or during contact with theorganic material to be converted as described hereinafter.

The conjugate Friedel-Crafts acids of this invention can be prepared byreacting the chalcogen compound-sulfuric acid component with one or moretransition metal halides. The reaction can be conducted by dissolvingthe chalcogen compound-sulfuric acid component in a polar solvent suchas those described above and dissolving or dispersing the transitionmetal halide in the resulting solution. Agitation and elevatedtemperatures, such as temperatures within the range of about 90° toabout 150° F., increase the rate of formation of the conjugate acid,i.e., the combination of the mono-adduct and transition metal halide.

The reactant-containing compositions of this invention can be preparedby mixing one or more organic and/or inorganic reactants, such as thosediscussed hereinafter, with one or more of the chalcogencompound-sulfuric acid components useful in the methods of thisinvention, including the conjugate Friedel-Crafts catalysts of thisinvention, in the presence or absence of an added solvent or surfactant.These compositions can be either homogeneous solutions or heterogeneousmixtures including liquid-liquid, solid-liquid and vapor liquid mixturesof the chalcogen compound-sulfuric acid and/or conjugate acid componentsand one or more liquid, solid or vaporous reactants.

The novel methods of this invention involve acid-catalyzed reactions oforganic compounds in the presence of a catalytically active amount ofthe described chalcogen compound-sulfuric acid components in thepresence or absence of additional components such as surfactants,transition metal halides, and/or the conjugate Friedel-Crafts catalystsof this invention, and reference to the chalcogen compound-sulfuric acidcomponents in the description of the methods of this invention isintended to include compositions which contain such additionalcomponents. The novel solvent and/or surfactant-containing compositionsare preferred in reactions involving relatively lipophilic organicmaterials since surfactants accentuate the activity of the chalcogencompound-sulfuric acid component toward such materials.

Any organic reaction that is catalyzed by relatively strong acids suchas sulfuric acid can be carried out by the methods of this invention. Avariety of such reactions are well known in the literature and many arediscussed in the Kirk-Othmer Encyclopedia of Chemical Technologypublication referred to above and the references referred to therein,the disclosures of which are incorporated herein by reference in theirentireties. Illustrative of such acid-catalyzed reactions are (1)oxidation, such as oxidative addition reactions; (2) reduction, such asreductive addition reactions; (3) esterification; (4)transesterification; (5) hydrogenation; (6) isomerization, includingracemization of optical isomers; (7) hydrolysis which, for the purposesof this disclosure, includes alcoholisis and thiolosis, i.e., thereaction of organic compounds with alcohols and thiols; (8) alkylation;(9) polymerization of olefinically unsaturated organic compounds; (10)Friedel-Crafts reactions; (11) demetalization; and (12) nitrationreactions. Other reactions that are known to be catalyzed by acidcatalysts can also be catalyzed by the chalcogen compound-sulfuric acidcomponents described herein. The specific methods discussed hereinaftercan be catalyzed by any one of the chalcogen compound-sulfuric acidcatalyst components discussed above including the surfactant and/ortransition metal halide-containing components.

Acid-catalyzed oxidative reactions primarily involve the abstraction ofhydrogen from an organic compound by reacting the compound with anoxidant. An illustrative example of such reactions is the oxidativeaddition of organic compounds illustrated by the following expression:

    R.sub.1 H+R.sub.2 H+1/2O.sub.2 →R.sub.1 R.sub.2 +H.sub.2 O (1)

wherein R₁ and R₂ are the same or different hydrocarbyl radicalsincluding straight and branched chain alkanes; alkenes; alkynes,aromatics; alkyl-, alkenyl-, and alkynyl-substituted aryls; andaryl-substituted alkanes, alkenes and alkynes, of essentially anymolecular weight, but usually having from 1 to about 40 carbon atoms permolecule. Preferred reactants include olefins, particularlyalpha-olefins.

The acid-catalyzed oxidation reactions can be promoted by contacting theorganic compound to be converted with the catalyst component in thepresence of an oxidant, which is preferably oxygen as illustrated in theabove equation. The oxidative addition reaction illustrated in theequation requires only that the organic compound contain acarbon-to-hydrogen bond capable of undergoing oxidative additionreactions. The organic compound can be either dispersed or dissolved ina melt or solution of the catalyst component in an appropriate solvent,or it can be contacted with the catalyst component by conventionalmixing and contacting procedures.

Acid-catalyzed reduction reactions of organic compounds in accordancewith the methods of this invention may involve the addition of hydrogento unsaturated organic compounds. Illustrative reactions include thehydrogenation of organic compounds containing olefinic, alkynyl oraromatic unsaturation, and reductive addition reactions such asdimerization, oligermerization and polymerization reactions asillustrated schematically in the following expression: ##STR4## whereinR₁, R₂, R₃ and R₄ are the same or different functional groups selectedfrom hydrogen and alkyl moieties having from 1 to about 20 carbon atoms.Preferred reactants including normal and branched chain alkenes andalkenyl aromatic compounds. The acid-catalyzed reduction reactions canbe conducted by contacting the organic compound to be converted with areducing agent such as hydrogen, hydrazine, and/or other reducingagents, in the absence of oxidants. Such reactions can be carried out byforming a composition such as a melt, solution or dispersion containingthe unsaturated organic compounds, the reducing agent, and the chalcogencompound-sulfuric acid component in the absence of oxidants underconditions of temperature and pressure sufficient to promote thereductive addition reaction. As illustrated by the examples discussedhereinafter, the reductive addition of propylene can be promoted atambient temperature.

Acid-catalyzed esterification reactions in accordance with the methodsof this invention typically involve reacting an esterifiable organiccompound having one or more amide, nitrile, carboxylic acid, carboxylicacid anhydride, acyl halide, and/or thiocarboxylic acid groups, with anorganic alcohol or thiol in the presence of the acid catalyst component.Such reactions can be conducted by contacting a composition containingthe chalcogen compound-sulfuric acid catalyst component, one or moreesterifiable organic compounds, and one or more alcohols, thiols and/oramines, under esterification conditions. Reactions of acids, amides andthioacids are illustrated by the following expression: ##STR5## whereinR₁ and R₂ are any organic radicals including natural and syntheticpolymers such as partially hydrolyzed protein or cellulose, nylon,dacron, etc., and Y and Z are the same or different divalent radicalsselected from oxygen, sulfur and NH groups. X is any integer of 1 orgreater and can range up to 1000 or more, depending upon the molecularweight of the compound involved. For instance, partially hydrolyzedpolymers such as those referred to above can contain 100 or morefunctional groups capable of undergoing esterification by theacid-catalyzed methods of this invention.

The reactions of alcohols, thiols, and amines with organic cyanides andacyl halides, while not illustrated in expression (3) above, arewell-known and can be promoted by the methods of this invention. Forinstance, the reaction of alcohols with acyl chlorides may be catalyzedby the method of the invention to form the corresponding ester andhydrogen chloride, and the reaction of organic cyanides with waterand/or alcohols results in the formation of the corresponding ester andammonia as discussed in Kirk-Othmer, Vol. 9, page 302. The evolution ofammonia by esterification of nitriles and amides may result in theconsumption of some of the sulfuric acid in the catalyst component butwill not prevent the occurrence of acid-catalyzed esterification.Sulfuric acid consumed by ammonia or by other bases produced or presentin esterification reactions (or in other acid-catalyzed reactionsencompassed by the methods of this invention) can be replaced by addingmakeup sulfuric acid during the process if desired.

Although expression (3) above indicates that all of the acyl moietiesare associated with one organic radical indicated by R₁, and that all ofthe alcohol, thiol and/or amine moieties are associated with one organicradical identified as R₂, that form of expression is employed only inway of illustration. For instance, a multifunctional carboxylic acid canbe esterified by a number of monofunctional alcohols; conversely, anumber of monofunctional carboxylic acids, thio-acids, etc., can beesterified by fewer molecules of a polyfunctional alcohol, thiol, etc.

Essentially any transesterification reaction can be conducted by themethods of this invention including (a) ester-ester interchange, (b)alcoholisis, which involves exchange of alcohol, thiol or amino groups,and (c) acidolysis which involves interchange of carboxylic acid,thiocarboxylic acid and/or amide groups. Such transesterificationreactions can be conducted by contacting a composition containing (1)the chalcogen compound-sulfuric component useful in this invention, (2)a carboxylic acid ester, thioester, and/or amido-ester, and (3) either(a) a dissimilar organoester, thioester and/or amide-ester, (b) acarboxylic acid, thioacid, or amide, (c) an alcohol, thiol, and/oramine, or (d) combinations of (a), (b) and (c), under esterificationconditions. Such reactions are illustrated schematically by thefollowing expressions: ##STR6## As in the case of esterificationillustrated by expression (3) above, the R₁, R₂, R₃ and R₄ moietiesinvolved in expressions 4(a), (b), and (c) can be the same or differentorganic moieties of essentially any molecular weight, Y and Z are thesame or different divalent radicals selected from oxygen, sulfur and NHgroups, and x represents any integer of 1 or greater. Also, as in thecase of esterification, compounds containing one or more ester groupscan be reacted either with mono- or polyfunctional esters, alcohols,thiols, acids, thioacids, etc. For instance, alcohols such as 1-butanolcan be reacted with either simple esters such as ethyl acetate toproduce butylacetate, or with complex polyamides, such as proteins, toproduce the corresponding butyl esters of aminoacids contained in theprotein.

The acid-catalyzed hydrogenation reactions of this invention can beconducted by contacting a composition containing (1) an organic compoundcontaining carbon-to-carbon unsaturation, (2) hydrogen, and (3) thechalcogen compound-sulfuric acid-containing catalyst under hydrogenationconditions. The reaction can be conducted by exposing a compositioncontaining the acid catalyst component, hydrogen, and an unsaturatedorganic compound under conditions of temperature and pressure sufficientto promote hydrogenation. The hydrogenation of olefins is illustrated byexpression (5).

    R.sub.1 --CH∛CH).sub.x R.sub.2 +xH.sub.2 →R.sub.1 --CH.sub.2 --CH.sub.2).sub.x R.sub.2                      ( 5)

wherein R₁ and R₂ are the same or different hydrogen or organic moietiesof essentially any molecular weight and x is any integer of 1 orgreater. For example, the methods of this invention can be employed tohydrogenate ethylene as well as polymers having molecular weights of100,000 or greater, which polymers contain a plurality of olefin bonds.They can also be employed to hydrogenate benzene, alkyl or alkenylaromatics, alkynes, and other unsaturated organic compounds.Olefinically unsaturated organic compounds, particularly hydrocarboncompounds, having 2 to about 40 carbon atoms are presently preferred.The hydrogenation reactions can be promoted by hydrogen, hydrazine, orother hydrogenating agents and are preferably conducted in the absenceof oxidizing agents such as oxygen and other oxidants.

The acid-catalyzed isomerization reactions involve the isomerization ofany organic compounds having 4 or more carbon atoms by contacting suchcompounds with the useful acid-catalyst component under isomerizationconditions. Such isomerization reactions can be conducted by contactinga composition containing the acid catalyst component and one or moreisomerizable organic compounds under isomerization conditions.Essentially any organic compounds can be isomerized by the methods ofthis invention including hydrocarbons and organic compounds containingelements other than carbon and hydrogen such as oxygen, sulfur,phosphorus, nitrogen, and the like. The existence of functional groupsin organic compounds employed in the acid-catalyzed isomerizationreactions of this invention which are reactive in the presence of theacid catalyst component may result in the occurrence of other reactionsin addition to isomerization. Nevertheless, isomerization will alsooccur.

The isomerization reactions encompassed by the methods of this inventionare particularly useful for the isomerization of relatively lowmolecular weight hydrocarbons having 4 to about 20 carbon atoms permolecule. They are also useful for the racemization of optical isomers,i.e., the conversion of dextro- or levorotatory isomers to thecorresponding racemic mixture.

The acid-catalyzed hydrolysis reactions include the reaction of water,alcohols or, thiols with (a) carboxylic acid amidoesters includingpolyamides; (b) carboxylic acid esters and polyesters such as proteins,i.e., polyamino acid esters; (c) thiocarboxylic acid esters andpolyesters; (d) ethers and thioethers including polyoxyethers andthioethers such as cellulose, rayon, starches, and otherpolysaccharides; (e) di- and poly-alkylamines including polyamines; (f)organic compounds containing olefinic unsaturation; and (g) epoxides.Such hydrolysis reactions can be conducted by contacting a compositioncontaining (1) the chalcogen compound-sulfuric acid component, (2) anorganic compound having one or more hydrolyzable functional groups suchas amido ester, acid ester, thioester, ether, thioether, amino,olefinic, and/or epoxy linkages, and (3) a hydrolyzing compound such aswater, alcohols and/or thiols under conditions of temperature andpressure sufficient to promote hydrolysis of the hydrolyzable functionalgroup. In the alternative, the organic compound containing ahydrolyzable functional group such as amido ester, acid ester, etc., canbe contacted with a composition containing the chalcogencompound-sulfuric acid-containing acid catalyst and a hydrolyzingcompound under hydrolyzing conditions.

Several of the hydrolysis reactions encompassed by this embodiment ofthe invention are also encompassed by the transesterification methods ofthis invention which involve alcoholosis as discussed above. Suchreactions include the reaction of alcohols and/or thiols with (1) mono-or polycarboxylic acid esters or polyesters; (2) mono- or polyfunctionalthiocarboxylic acid esters or polyesters; and (3) mono- orpolycarboxylic acid amido-esters or polyamido esters.

A particularly interesting aspect of the hydrolysis reactions which canbe effected in accordance with the methods of this invention is thatthey can be employed for either the partial or the complete hydrolysisof natural and synthetic polymers such as polysaccharides includingcellulose, starches, and the like, protein, rayon, nylon, and others, bycontacting such materials with the acid catalyst components of thisinvention containing water. Such reactions proceed even at ambienttemperature and, if allowed to go to completion, they result in completedepolymerization, i.e., complete hydrolysis of the polymer. For example,cellulose can be converted completely to glucose and proteins can beconverted to amino acids by this method. Hydrolysis of polysaccaharidesis discussed in more detail in my copending application Ser. No. 673,358referred to above the disclosure of which is incorporated herein byreference in its entirety. The partial hydrolysis of cellulose appearsto account for the dramatic herbicidal activity of the chalcogencompound-sulfuric acid components employed in the methods of thisinvention, and the herbicidal activity of urea-sulfuric acid componentsis discussed in more detail in my copending application Ser. No.444,667. The ability of surfactants to accentuate the activity of theurea-sulfuric acid component and to broaden the variety of vegetationcontrolled is also discussed in said copending application. The otherchalcogen compound-sulfuric acid components exhibit similar herbicidalactivity when combined with surfactants.

The hydrolysis reactions are illustrated, in part, by the followingexpressions which are intended only to be schematic representations ofseveral of the acid-catalyzed hydrolysis reactions encompassed by themethods of this invention: ##STR7##

Expression 6(a) represents the complete acid-catalyzed hydrolysis ofamino acid esters, including poly-amino acid esters such as proteins, byreaction with a hydrolyzing agent. In accordance with expression 6(a),R₁ can be any difunctional organic moeity, Y can be hydrogen or amono-functional terminal inorganic moiety such as potassium or othermetal ion, R₂ is hydrogen or any organic moiety including hydrocarbylradicals having 1 to 20 carbon atoms per molecule, X is oxygen, sulfur,nitrogen, or a combination of these, and n is any integer of 1 orgreater. From expression 6(a) it can be seen that the reaction ofprotein--a poly-alphaamino acid ester--with water, if allowed to go tocompletion, results in formation of the amino acid monomer unitscontained in the protein. Expression 6(b) illustrates the hydrolysis ofa diorganoamine by reaction with an organ-thiol in which R₁, R₂, and R₃can be any organic moiety.

Expression 6(c) illustrates the hydrolysis of an organic thioester byreaction with water to produce the corresponding carboxylic acid andthiol in which R₁ and R₂ can be any organic moeity. As in the case ofthe other hydrolysis reactions encompassed by this embodiment of theinvention, alcohols and/or thiols can be substituted for, or combinedwith, the water illustrated in expression of 6(c).

Expression 6(d) schematically illustrates the hydrolysis of an organicepoxide by the acid-catalyzed reaction of the epoxide with water, thiolsor alcohols, in which R₄ and R₅ are monovalent moieties selected fromhydrogen and any Organic moiety, R₆ is a monovalent organic moietyhaving at least one carbon, and X is selected from oxygen, sulfur andnitrogen.

The hydrolysis of olefins, including poly-functional olefins, withwater, alcohols or thiols, can be illustrated schematically by thefollowing expression: ##STR8## in which R₁ and R₂ and R₃ are the same ordifferent monovalent moieties selected from hydrogen and any organicmoiety, X is O, S, and/or NH, and n is any integer of 1 or greater.

Alkylation reactions in accordance with the methods of this inventioninclude the reaction of any organic compound capable of being alkylatedby acid-catalyzed reaction with an organic reactant containing olefinicunsaturation. These reactions can be effected by contacting thealkylatable organic compound with a composition comprising the chalcogencompound-sulfuric acid-containing acid catalyst and an organic reactantcontaining olefinic unsaturation, and are illustrated schematically bythe following expression: ##STR9## wherein R₂ and R₃ are the same ordifferent hydrogen or organic moieties, particularly alkyl groups havingfrom 1 to 10 carbon atoms, and R₁ is an alkylatable organic compound,particularly straight or branched chain alkanes, aromatics,alkyl-aromatics, and/or aryl-alkanes having from 4 to 20 carbon atomsper molecule.

Acid-catalyzed olefin polymerization reactions include thepolymerization of at least one organic compound containing at least onecarbon-to-carbon olefin bond capable of undergoing acid-catalyzedpolymerization by contacting the organic compound or compounds with thesulfuric acid-containing catalyst of this invention. In this embodiment,the reaction system is preferably substantially oxidant-free. Suchpolymerization reactions are illustrated schematically by the followingexpression: ##STR10## in which R₁ and R₂ are selected from hydrogen ormonovalent organic moieties, particularly hydrocarbyl radicals havingfrom 1 to 10 carbon atoms, and n is the number of monomer unitsincorporated in the polymer. Copolymers of two or more olefinicallyunsaturated monomers can be produced. Illustrative of such copolymersare styrene-butadiene, ethylene-propylene, methacrylic acid-ethylacrylate-hydroxyethylacrylate, and ethylene-dicyclopentadienecopolymers, and the like, including the so-called hydrocarbon resinsderived from cracked petroleum distillates, turpentine fractions, coaltar fractions and certain olefinic monomers, such as the hydrocarbonresins discussed in Kirk-Othmer, Volume 12, at pages 852-857 and in thereferences cited therein.

The Friedel-Crafts reactions involve the reaction of organic compounds,particularly hydrocarbon compounds, capable of undergoing acid-catalyzedFriedel-Crafts reactions, with hydrocarbyl halides. Such reactions canbe effected by contacting one or more organic compounds with acomposition comprising the sulfuric acid-containing catalyst and ahydrocarbyl halide. Such Friedel-Crafts reactions are illustratedschematically by the following expression:

    R.sub.1 H+R.sub.2 X→R.sub.1 R.sub.2 +HX             (10)

in which R₁ is a monovalent organic moiety capable of undergoingFreidel-Crafts reactions with hydrocarbyl halides, R₂ is a monovalenthydrocarbyl moiety, preferably an alkyl group having from 1 to 20 carbonatoms, and X is a halogen, preferably chlorine, bromine or fluorine,most preferably chlorine.

The acid-catalyst component employed to catalyze the Friedel-Craftsreactions can comprise any of the described chalcogen compound-sulfuricacid components, although the acid components which contain aFriedel-Crafts halide catalyst such as the novel conjugateFriedel-Crafts catalysts of this invention, are preferred.

The acid-catalyzed demetalization reactions include the demetalizationof organo-metal compounds capable of undergoing acid-catalyzeddemetalization by reaction with water and/or alcohols, and they can beeffected by contacting a composition containing such organo-metalcompounds, the described sulfuric acid-containing catalyst and waterand/or alcohols, under conditions of time and temperature sufficientdemetalization reactions are illustrated by the following expression:##STR11## wherein R is any organic radical including porphyrins andpetroporphyrins, M is any metal, and a is the valence of the metalassociated with the organic moiety. Organic complexes of zero-valentmetals can also be demetalized by these methods. Illustrative of theorgano-metal compounds that can be demetalized by reaction with waterand/or alcohol in accordance with these methods are the porphyrins andpetroporphyrins commonly found in petroleum crudes, tarsand oils, shaleoils, coal extracts, and the like.

The acid catalyzed demetalization reactions can be conducted in thepresence of an oxidant such as oxygen, peroxides, ozone, and the like,to oxidize the metal contained in the organo-metal compound to a moresoluble, higher valence state when desired. Such oxidativedemetalization conversions can be effected by contacting a compositioncontaining the organo-metal compound, the chalcogen compound-sulfuricacid component, and the oxidant. Similarly, the valence state of themetal complexed in the organo-metal compound can be reduced to produce amore soluble metal ion, e.g., the conversion of ferric to ferrous iron,by conducting the acid-catalyzed demetalization reaction in the presenceof a reducing agent such as hydrogen, hydrazine, and the like. Suchreductive acid-catalyzed demetalization reactions can be conducted bycontacting a composition containing the organo-metal compound, thechalcogen compound-sulfuric acid component, and a reducing agent.

The acid-catalyzed nitration reactions of this invention involve thereaction of organic compounds capable of undergoing acid-catalyzednitration with nitrogen oxides, particularly with nitric oxide, and canbe effected by contacting a composition containing the nitratablecompound, nitrogen oxides, and the chalcogen compound-sulfuricacid-containing catalyst under nitration conditions. Such reactions areillustrated schematically by expression (12).

    R(H).sub.n +nNO.sub.2 →(NO.sub.2).sub.n R+.sub.n H.sup.+( 12)

in which R is any nitratable organic moiety having a valence of n.Illustrative of nitration reactions that be conducted in accordance withthis invention are the reaction of toluene with nitric oxide to producenitrotoluene and trinitrotoluene (TNT), the nitration of cellulose toproduce nitrocellulose, the nitration of alkanes such as n-decane, andthe like.

The acid-catalyzed organic reactions discussed above, and otheracid-catalyzed reactions known in the art, can be effected by contactingthe organic material to be reacted in either vapor phase, liquid phase,or solid phase (as in the case of cellulose, nylon and other solidmaterial), with the liquid or solid chalcogen compound-sulfuricacid-containing catalyst. The liquid catalysts can comprise a melt ofthe anhydrous chalcogen compound-sulfuric acid catalyst component, or itcan comprise a solution of that component in either the organic feedmaterial or other solvent. The solid catalysts can comprise thechalcogen compound-sulfuric acid component, with or without thedescribed optional components, impregnated or ion-exchanged into a solidsupport. Mixed liquid phase reactions can be conducted by formingemulsions or dispersions of the chalcogen compound-sulfuric acidcomponent melt or solution and the reactants and/or organic material tobe converted. The novel surfactant-containing chalcogencompound-sulfuric acid components of this invention are particularlysuitable for use as acid catalysts in the conversion of organicmaterials containing significant amounts of lipophilic substances suchas waxes, oils, and high molecular weight organic substances.Illustrative of such lipophilic materials are the waxy cuticle on manytypes of vegetation, proteins, particularly fat-containing proteins,cellulosic substrates containing ligands and other lipophilic substancesderived from wood, and the like.

The acid-catalyzed reactions of this invention can be conducted at anytemperature below the thermal decomposition temperature of the chalcogencompound-sulfuric acid component and above that temperature at which thecomposition comprising the chalcogen compound-sulfuric acid componentsolidifies. The reaction temperature should also be maintained below thetemperature at which the organic feed material, reactants,intermediates, or products react with the chalcogen compound-sulfuricacid component. The occurrence of any such side reactions at any givenreaction temperature can be readily determined by analyzing the productto determine the presence of by-products resulting from such sidereactions. For instance, reaction temperatures used with theurea-sulfuric acid components should be maintained below 176° F. andpreferably below about 170° F. in reactions in which a significantamount of water is present due to the relatively low decompositiontemperature of the urea-sulfuric acid component in the presence ofwater. Higher reaction temperatures up to about 300° F. can be employedwith urea-sulfuric acid components under anhydrous conditions when thereaction system is substantially free of water, i.e., when the systemcontains less than about 2, preferably less than about 1 weight percentwater based on the concentration of urea-sulfuric acid component.However, such higher temperatures, i.e., temperatures above 170° F., arepreferably avoided unless the reaction system is essentially water-free,i.e., does not contain any detectable amount of water. Reaction rateincreases as temperature is increased. The thermal decompositiontemperature of other hydrous and anhydrous chalcogen compound-sulfuricacid components can be readily determined by gradually increasing thetemperature of the selected composition until evidence of decompositionoccurs such as effervescence or other vapor evolution and discoloration.

The methods of this invention can be conducted at essentially anypressure and even under vacuum if desired. Vapor phase reactions, i.e.,reactions involving organic reactants in the vapor phase, can beaccelerated by increasing the pressure on the system. Illustrativereaction pressures are 0 to 2,000 atmospheres although pressures of 0 to100 atmospheres are usually sufficient to achieve acceptable reactionrates.

The acid-catalyzed reactions of this invention require contact times ofthe organic reactants and the sulfuric acid-containing componentcommensurate with the desired product yield. Generally, increasing thecontact time increases the conversion. Since reaction rate depends uponthe nature of the reaction involved, the compatibility of the sulfuricacid-containing component with the reactants, and the operating pressureand temperature, the reaction time should be sufficient to obtain thedegree of conversion required. Batch contact times of one minute to 100hours are usually sufficient to accomplish complete conversion of mostorganic substrates. Shorter reaction times will usually be involved incontinuous processes employing the methods of this invention in whichcase it may be desirable to separate unreacted organic materials fromthe effluent of the reaction zone and to recycle those materials to thereaction zone.

The novel compositions and acid-catalyzed methods of converting organiccompounds in accordance with this invention have several significantadvantages over compositions and methods otherwise available to the art.The chalcogen compound-sulfuric acid components are relativelyinexpensive; in addition, they are non-corrosive and stable under normalconditions. They are also highly active protonating agents and thereforecan be employed to effect the acid-catalyzed conversion of a widevariety of organic compounds without promoting reactions associated withother acid catalysts, particularly side reactions associated with theuse of sulfuric acid such as oxidation and sulfonation.

The invention is further described by the following examples which areillustrative of specific modes of practicing the invention and are notintended as limiting the scope of the invention as defined by theappended claims.

EXAMPLE 1

This example illustrates the hydrolysis of complex polyethers bydemonstrating the complete hydrolysis of cellulose to glucose in thepresence of a urea-sulfuric acid component of this invention. Sterilecotton swabs are dissolved in a urea-sulfuric acid component having aurea/sulfuric acid molar ratio of 1.2 and containing 38.6 weight percenturea, 52.1 weight percent sulfuric acid, and 8.3 weight percent waterwhich is maintained at a temperature of 70° F. The cotton swabs areadded sequentially to approximately 500 ml. of the describedurea-sulfuric acid component, and the mixture is stirred throughout theoperation. Complete dissolution of each cotton swab occurs inapproximately one minute. After the addition of approximately 20 cottonswabs the mixture become more viscous. A quantity of the reactantmixture is analyzed by high precision liquid chromatography (HLPC) andis found to contain glucose in an amount which corresponds to thestoichiometric conversion of the cellulose feed to the reaction. Neitherthe HLPC analysis nor any other observation during the operationindicates the occurrence of any reaction other than the hydrolysis ofcellulosic to glucose. There is no evidence of sulfonation or oxidationof either the cellulose or glucose. No fumes are emitted and thereaction medium does not discolor during the process.

EXAMPLE 2

This example illustrates the use of a urea-sulfuric acid component ofthis invention to acid-catalyze the hydrolysis of cellulose in livingvegetation and the consequent efficacy of the chalcogencompound-sulfuric acid components as herbicides.

Four replicated test plots of five acres each comprising onions at thefirst true-leaf stage (approximately one-inch high) infested with malva,cheese weed, nightshade, shephards purse, peneapple weed and purslane,are each treated by foliar application of 50 gallons per acre of aurea-sulfuric acid component having a urea/sulfuric acid molar ratio ofapproximately 1.1 and containing 14.6 weight percent urea, 20.8 weightpercent sulfuric acid and 64.6 weight percent water. The describedtreatment results in 95 to 100 percent kill of all weed species within48 hours after application. There is no damage to the onion crop asevidenced by the lack of foliage browning, spotting, or the like. Thecellulosic structure of the onion crop is protected by the waxy cuticlecharacteristic of green onions, which, however, can also be hydrolyzedby the use of the surfactant-containing chalcogen compound-sulfuric acidcomponents within the scope of this invention.

EXAMPLE 3

This example illustrates the hydrolysis of polycarboxylic acid estersand demonstrates the depolymerization of protein by contact with thechalcogen compound-sulfuric acid components of this invention. Twocowhide pump seals are contacted with a urea-sulfuric acid componentcontaining 36.5 weight percent urea, 52.1 weight percent sulfuric acidand 11.4 weight percent water having a urea/sulfuric acid molar ratio ofabout 1.1 for approximately 70 hours at room temperature. The cowhideseals completely dissolve within the 70-hour contact period.

EXAMPLE 4

The operation of Example 3 is repeated by contacting two cowhide pumpseals with a urea-sulfuric acid component containing 21.5 weight percenturea, 55.2 weight percent sulfuric acid and 23.3 weight percent waterhaving a urea/sulfuric acid molar ratio of about 0.6. This compositionscorresponds to the formulation 10-0-0-18. The cowhide pump sealscompletely dissolve within 70 hours at room temperature.

EXAMPLE 5

This example illustrates the oxidative addition of organic compounds anddemonstrates the oxidative addition of propylene in the presence of thechalcogen compound-sulfuric acid components of this invention. Technicalgrade propylene and air are introduced into approximately 1000 ml. of aurea-sulfuric acid component containing 38.6 weight percent urea, 52.1weight percent sulfuric acid and 9.3 weight percent water having aurea/sulfuric acid molar ratio of 1.2. The gas mixture is introducedthrough a sparger submerged in the urea-sulfuric acid component which ismaintained at 70° F. and is contained in a three-neck five-liter flaskprovided with agitation, and feed inlet and exit means. The vaporeffluent from the liquid phase is removed from the five-liter flask andpassed to an ice-cooled liquid trap in which the reaction products arecollected. The liquid phase recovered from the vapor effluent isanalyzed by infrared spectroscopy and is found to contain propylenedimers and higher oligimers of propylene containing olefinicunsaturation.

EXAMPLE 6

Propylene and butene are reductively added to each other by introducinggaseous propylene and 2-butene into the liquid phase formed by meltingan anhydrous urea-sulfuric acid component containing 42.6 weight percenturea and 57.4 weight percent sulfuric acid having a urea-sulfuric acidmolar ratio of 1.2. The liquid phase is maintained at a temperature of150° F. and the vapor and liquid phases are maintained at a pressure of1000 psig. The liquid phase is continuously removed from the reactionzone and flashed to recover vaporizable dimers and higher polymers ofpropylene and 2-butene, and co-polymers of propylene and 2-butene.Higher polymers that are not removed by flashing can be extracted fromthe urea-sulfuric acid melt with normal hexane at a pressure sufficientto maintain the normal hexane in the liquid phase. The recoveredurea-sulfuric acid component is recycled to the reaction zone.

EXAMPLE 7

Maleic acid is reacted with 1,2-ethanediol (glycol) by agitating a 50-50molar mixture of maleic acid and glycol with a urea-sulfuric acidcomponent containing 36.5 weight percent urea, 52.1 weight percentsulfuric acid and 11.4 weight percent water having a urea/sulfuric acidmolar ratio of 1.1 at a temperature of 140° F. under a pressure of 100psig. for 10 minutes to produce the corresponding polyester of maleicacid and 1,2-ethanediol. The resulting polymer is extracted from thereaction phase with isopropyl alcohol.

EXAMPLE 8

Benzene is alkylated with a mixture of 1-butene and 2-butene to producenormal and isobutylbenzenes by agitating a mixture of benzene, 1-buteneand 2-butene with a molten urea-sulfuric acid component containing 42.6weight percent urea and 57.4 weight percent sulfuric acid in thepresence of an alkyl phenol polyethylene oxide surfactant at atemperature of 160° F. and under a reaction pressure sufficient tomaintain the reactants in the liquid phase. The resulting alkylbenzeneis recovered by centrifuging the resultant reaction phase mixture.Complete separation is achieved by washing the urea-sulfuric acidcomponent melt with toluene.

EXAMPLE 9

Normal-butylbenzene is prepared by heating equal molar amounts of1-chlorobutane and benzene in a molten urea-sulfuric acid componentcontaining 42.6 weight percent urea and 75.4 weight percent sulfuricacid having a urea/sulfuric acid molar ratio of 1.2 at a temperature of140° F. and a pressure of 100 psig. for a period of 10 minutes. Then-butylbenzene product is recovered by cooling the reaction mixture tosolidify the urea-sulfuric acid component melt and extracting theresulting mixture with toluene. The n-butyl-benzene product is removedfrom the toluene solvent by distilling the solvent, and theurea-sulfuric acid component is re-melted and recycled to the process.

EXAMPLE 10

A mixture of isooctanes is prepared by contacting normal octane with amolten urea-sulfuric acid component containing 42.6 weight percent ureaand 57.4 weight percent sulfuric acid and having a urea/sulfuric acidmolar ratio of 1.2 at a temperature of 160° F. under a pressure of 500psig. for 5 minutes. The resulting isooctane mixture is recovered bycooling the melt to a temperature of 70° F. to solidify the moltenmixture and extracting the isooctane product with normal hexane. Theresulting solution of hexane and isooctane is separated by distillationand the urea-sulfuric acid is melted and returned to the reaction zone.

EXAMPLE 11

A petroleum crude oil containing organo-metal compounds comprisingpetroporphyrins is demetalized by contacting the petroleum crude oilwith an aqueous urea-sulfuric acid component containing 36.5 weightpercent urea, 52.1 weight percent sulfuric acid and 11.4 weight percentwater having urea/sulfuric acid molar ratio of 1.1 in the presence ofoxygen at a temperature of 160° F. and a pressure of 500 psig. withsufficient agitation to intimately mix the petroleum crude oil and theurea/sulfuric acid component. The recovered by decanting from theurea-sulfuric acid component, water washed to remove residual urea,sulfuric acid and metal salts, and dried by distillation.

EXAMPLE 12

Benzene is nitrated by forming a dispersion of benzene in a solution ofa urea-sulfuric acid component having a urea/sulfuric acid molar ratioof 1.1 and containing 15.9 weight percent urea and 22.7 weight percentsulfuric acid in water with sufficient agitation to produce an intimatedispersion of the benzene and the urea-sulfuric acid component solution.Nitric oxide is dispersed into the agitated mixture of benzene and theurea-sulfuric acid component, and the resulting mixture is contacted ata temperature of 150° F. and a pressure of 200 psig. The resultingnitrated benzene product is recovered by cooling the reaction mixtureand extracting the nitrated benzene product with toluene.

EXAMPLE 13

The mono-N-allyl thioformamide adduct of sulfuric acid is prepared byplacing 50 grams of N-allyl thioformamide in a 500 ml. flask along with200 ml. of diethylether, chilling to 50° F. and then gradually adding 51grams of 98 percent sulfuric acid pre-chilled to 30° F. at a ratesufficiently slow to maintain the mixture in the flask at a temperaturebelow 50° F. 200 ml. water is added to the flask and the mixture isallowed to equilibrate to room temperature (70° F.). Cotton swabs arethen immersed in the mixture at room temperature and maintained for 24hours to hydrolyze the cotton cellulose.

EXAMPLE 14

21 grams of 98 weight percent sulfuric acid and 50 grams of1-(4-aminobenzenesulfonyl)-2-thiourea are mixed by the proceduredescribed in Example 13 to produce the corresponding equimolar adductdissolved in the ether-water mixture which can then be employed tohydrolyze cellulose.

EXAMPLE 15

30 grams of 98 weight percent sulfuric acid and 50 grams of1-benzoylurea are mixed by the procedure described in Example 13 to formthe corresponding equimolar adduct dissolved in the ether-water mixturewhich can be employed to hydrolyze cellulose.

EXAMPLE 16

15.5 grams of 98 weight percent sulfuric acid and 50 grams of1,3-bis(2-ethoxyphenyl) carbamide are mixed by the procedure describedin Example 13 to form the corresponding equimolar adduct dissolved inthe ether-water mixture which can be employed to hydrolyze cellulose asdescribed in Example 13.

EXAMPLE 17

22 grams of 98 weight percent sulfuric acid and 50 grams of1-(2-bromo-3-methylbutanoyl) carbamide are mixed by the proceduredescribed in Example 13 to produce the corresponding equimolar adductdissolved in the ether-water mixture which can be employed to hydrolyzecellulose.

EXAMPLE 18

23 grams of 98 weight percent sulfuric acid and 50 grams of1-(4-bromophenyl) carbamide are mixed by the procedure described inExample 13 to form the corresponding equimolar adduct dissolved in theether-water solution which can be employed to hydrolyze cellulose asdescribed in Example 13.

EXAMPLE 19

34 grams of 98 weight percent suIfuric acid and 50 grams of 1,3-diacetylcarbamide are mixed by the procedure described in Example 13 to form thecorresponding equimolar adduct dissolved in the ether-water solution.Propylene and air are then bubbled through the solution at a temperatureof 90° F. and a pressure of 500 psi. to form proplene dimers and higheroligomers.

EXAMPLE 20

32.5 grams of 98 weight percent sulfuric acid and 50 grams of1-ethyl-2-selenourea are mixed by the procedure described in Example 13to form the corresponding equimolar adduct dissolved in the ether-watersolution. Cowhide pump seals can be emerged in the solution maintainedfor 24 hours at 100° F. to partially hydrolyze the cowhide protein.

While particular embodiments of this invention have been described, itwill be understood, of course, that the invention is not limited theretosince many obvious modifications can be made and it is intended toinclude within this invention any such modifications as will fall withinthe spirit and scope of the appended claims.

I claim:
 1. A method for isomerizing hydrocarbons having 4 to about 20carbon atoms, which comprises contacting said hydrocarbons underisomerization conditions with a catalytically active amount of acatalyst comprising the monoadduct of sulfuric acid and achalcogen-containing compound having the empirical formula ##STR12##wherein X is oxygen or sulfur, each of R₁ and R₂ is selected from thegroup consisting of hydrogen, NR₃ R₄ and NR₅, at least one of R₁ and R₂is other than hydrogen, each of R₃ and R₄ is selected from the groupconsisting of hydrogen and monovalent organic radicals, and R₅ is adivalent organic radical.
 2. A method for isomerizing hydrocarbonshaving 4 or more carbon atoms, which comprises catalyzing said reactionunder isomerization conditions with a catalyst comprising the monoadductof sulfuric acid and a chalcogen-containing compound having theempirical formula ##STR13## wherein X is O or S, each of R₁ and R₂ isindependently selected from hydrogen and NR₃ R₄, at least one of R₁ andR₂ is other than hydrogen, each of R₃ and R₄ is independently selectedfrom hydrogen and monovalent organic radicals.
 3. A method forisomerizing hydrocarbons having 4 or more carbon atoms, which comprisescontacting said hydrocarbons under isomerization conditions with acatalyst consisting essentially of the monoadduct of sulfuric acid and achalcogen-containing compound having the empirical formula ##STR14##wherein X is O or S, each of R₁ and R₂ is independently selected fromhydrogen, NR₃ R₄, and NR₅, at least one of R₁ and R₂ is other thanhydrogen, each of R₃ and R₄ is independently selected from hydrogen andmonovalent organic radicals, R₅ is a divalent organic radical, and saidcomposition is free of sulfuric acid.
 4. The method defined in any oneof claims 1, 2 or 3, wherein said catalyst is essentially free ofthermal decomposition products of sulfuric acid or saidchalcogen-containing compound.
 5. The method defined in any one ofclaims 1, 2 or 3, wherein said reaction is carried out at a temperaturebelow the thermal decomposition temperature of said monoadduct.
 6. Themethod defined in any one of claims 1 or 2 wherein said reaction isconducted in the presence of a solution containing at least about 1weight percent of said adduct, and said catalyst consists essentially ofsaid adduct.
 7. The method defined in any one of claims 1, 2 or 3,wherein said catalyst is substantially anhydrous.
 8. The method definedin any one of claims 1, 2 or 3, wherein said catalyst comprises about 1weight percent water or less.
 9. The method defined in any one of claims1 or 2, wherein said adduct constitutes at least about 80 weight percentof said catalyst.
 10. The method defined in any one of claims 1, 2 or 3,wherein said catalyst comprises a member selected from the groupconsisting of surfactants, solvents other than water, and combinationsthereof.
 11. The method defined in any one of claims 1, 2 or 3, whereinsaid catalyst is a solid, and said reaction is conducted by contactingsaid hydrocarbon with said solid catalyst.
 12. The method defined in anyone of claims 1, 2 or 3, wherein R₁ and R₂ are independently selectedfrom hydrogen and NR₃ R₄.
 13. The method defined in any one of claims 1,2 or 3, wherein R₁ and R₂ are independently selected from hydrogen andNR₃ R₄, R₃ and R₄ are independently selected from H and monovalenthydrocarbyl radicals, and R₇ and R₈ are independently selected fromhydrogen and hydrocarbyl radicals having 1 to about 10 carbon atoms. 14.The method defined in any one of claims 1, 2 or 3, wherein R₁ and R₂ areindependently selected from hydrogen and NR₃ R₄, and R₃ and R₄ areindependently selected from hydrogen and hydrocarbyl radicals having upto about 10 carbon atoms.
 15. The method defined in any one of claims 1,2 or 3, wherein R₁ and R₂ are independently selected from hydrogen andNR₃ R₄, R₃ and R₄ are independently selected from hydrogen andhydrocarbyl radicals having up to about 10 carbon atoms, and saidreaction is conducted under isomerization conditions including atemperature of up to about 300° F., a pressure of 0 to 100 atmospheresand a reaction time of about 1 minute to about 100 hours sufficient toisomerize a substantial proportion of said hydrocarbon.
 16. The methoddefined in claim 15 wherein said chalcogen-containing compound comprisesa member selected from the group consisting of urea, thiourea,formamide, and combinations thereof.